CN101321774B - Process for preparing ortho-metallated metal compounds - Google Patents

Process for preparing ortho-metallated metal compounds Download PDF

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CN101321774B
CN101321774B CN2006800458117A CN200680045811A CN101321774B CN 101321774 B CN101321774 B CN 101321774B CN 2006800458117 A CN2006800458117 A CN 2006800458117A CN 200680045811 A CN200680045811 A CN 200680045811A CN 101321774 B CN101321774 B CN 101321774B
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carbon atom
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CN101321774A (en
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菲利普·斯托塞尔
罗科·福特
埃米尔·帕勒姆
埃丝特·布罗伊尼希
霍尔格·海尔
霍斯特·维斯特韦伯
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    • C07F17/00—Metallocenes
    • C07F17/02—Metallocenes of metals of Groups 8, 9 or 10 of the Periodic System
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    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
    • C07F15/0033—Iridium compounds
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    • C—CHEMISTRY; METALLURGY
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    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
    • C07F15/0046—Ruthenium compounds
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    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
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    • C07F15/006—Palladium compounds
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    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
    • C07F15/0073—Rhodium compounds
    • C—CHEMISTRY; METALLURGY
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    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
    • C07F15/0086—Platinum compounds
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
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    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/30—Coordination compounds
    • H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
    • H10K85/342—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising iridium

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Abstract

The present invention describes a process for preparing homoleptic and heteroleptic tris-ortho-metallated metal compounds which, in their capacity as functional materials, find use as colouring components in a range of diverse applications attributable in the widest sense to the electronics industry.

Description

The method for preparing ortho-metalated metallic compound
The invention describes from simple starting compound preparation and all join type and different method of joining the tris-ortho-metalated metallic compound of type.
Organometallic compound, particularly d 8The compound of metal can be used as the functional materials of the many different application that the most broadly belong to electronic industry.The general structure of organic electroluminescence device and their stand-alone assembly one Organic Light Emitting Diode (OLEDs) is described among US 4539507 and the US 5151629.Research and development in this respect be to use the organometallic complex that shows phosphorescence rather than fluorescence (M.A.Baldo etc., Appl.Phys.Lett.1999,75,4-6).From the reason of spin statistics, energy and the power efficiency of using the organometallic compound realization to be up to four times are possible.These research and development appear to confirm itself to be superior to the singlet twinkler, are such for red and green emitting at least.
For this purpose, must might obtain the effective chemical route of synthesis of corresponding high purity organometallic compound.This utilizes this compounds for resources conservation property is vital, particularly considers the scarcity of rear transition metal Rh, Ir, Pd and Pt.
For with the corresponding metal title complex as for the monomer of preparation oligopolymer and polymkeric substance, need the effective way of the corresponding functionalized metal complexes of acquisition equally.These special demands can obtain carrier band polymerizable groups on or two ligands in a suitable manner and the three-fold coordination body not by polymerisable group functionalization's the different shaped metal title complex of joining.
The certain methods for preparing tris-ortho-metalated organo-iridium compounds has been described in document.Below with reference to the precursor structure of this compounds, three [2-(2-pyridyl-κ N) phenyl-κ C] iridium (III) is sketched this synthetic synthetic route, productive rate and characteristic.
Begin from hydration iridium chloride (III) and 2-phenylpyridine ethoxy ethanol/water (3: 1) mixture, after handling, obtained the face formula-three as by product [2-(2-pyridyl-κ N) phenyl-κ C] iridium (III) of productive rate about 10% with complicated chromatogram method of purification; And the principal product that obtains is the complex of iridium (K.A.King of dichloro bridge joint; P.J.Spellane, R.J.Watts, J.Am.Chem.Soc.1985; 107,1431-1432).
People such as K.Dedeian have described since three (acetylacetonate) iridium (III) and 2-phenylpyridine, obtain the method for face formula-three [2-(2-pyridyl-κ N) phenyl-κ C] iridium (III) of productive rate 45% thus.In the method, this product also must be removed impurity through the sorptography purifying, and this method is used halohydrocarbon simultaneously.(K.Dedeian，P.I.Djurovich，F.O.Garces，G.Carlson，R.J.Watts，Inorg.Chem.1991，30，1685-1687)。
In other method, two-μ-chlorine four [2-(2-pyridyl-κ N) phenyl-κ C], two iridium (III) are as starting material, and at first iridium chloride (III) and the 2-phenylpyridine from hydration prepares; About 72% (S.Spouse, K.A.King, the P.J.Spellane of productive rate; R.J.Watts; J.Am.Chem.Soc.1984,106,6647-6653).This is a 2-phenylpyridine and based on two-μ-chlorine four [2-(2-pyridyl-κ N) phenyl-κ C], two iridium (III), the reaction of the silver triflate of twice molar weight.After chromatogram purification, the author obtain productive rate be 75% face formula-three [2-(2-pyridyl-κ N) phenyl-κ C] iridium (III) (M.G.Colombo, T.C.Brunold, T.Riedener, H.U.G ü del, Inorg.Chem.1994,33,545-550).Except that chromatogram purification, it uses halohydrocarbon to carry out equally, and it is disadvantageous using silver triflate, because the silver of trace is difficult to from product, remove, and the photoelectric properties of this complex of iridium is had a negative impact.
People such as M.Thompson have described the face formula and through synthetic (A.B.Tamayo, B.D.Alleyne, the P.I.Djurovich of formula three [2-(2-pyridyl-κ N) phenyl-κ C] iridium (III); S.Lamansky, I.Tsyba, N.N.Ho; M.E.Thompson; J.Am.Chem.Soc.2003,125,7377-7387).For this purpose, two-μ-chlorine four [2-(2-pyridyl-κ N) phenyl-κ C] iridium (III) heats in glycerine with phenylpyridine, adds salt of wormwood simultaneously.About 200 ℃ temperature of reaction obtains the complex of iridium of face formula, and 140-145 ℃ temperature of reaction obtains the complex of iridium through formula.Productive rate is 65-80% under two kinds of situation.Under two kinds of situation, all form product mixtures, wherein must separate this pure title complex, meaning this method and be not suitable for industrial use through chromatography.
This method of in WO 02/060910, describing is in the dipolar aprotic solvent existence and is forcing under the heat; Make three (acetylacetonate) iridium (III) and similar 1, the long-time (＞20h) reaction that 3-ketone ketone acid salt complex and aryl-pyridine or heteroaryl pyridine compounds carry out.Fabulous productive rate (being up to 96%) and fabulous purity (＞99.9%) have been obtained here.Yet, disadvantageous be this synthetic must be since three (acetylacetonate) iridium (III), and it at first must prepare other synthesis step from iridium chloride.The productive rate of preparation three (acetylacetonate) iridium of in document, enumerating (III) only is about 25%, is meaning generally speaking to have occurred sizable iridium loss here.For the method among the WO04/085449, situation too, this method begins from the different type complex of iridium of joining, described different type complex of iridium carrier band two acetylacetonate types ligand and two other halogenide type ligands of joining.Also obtained ortho-metalated metal complexes with high yield and purity here, but the initial title complex of this iridium must synthesize in other step, this causes the loss of productive rate equally.In addition, these two kinds of methods are not suitable for preparing different metal complexes of joining type.
WO 04/099223 has described in the presence of silver, mercury, aluminium or antimonic salt, prepares the method for tris-ortho-metalated complex of iridium through ligand and the reaction of halogenation iridium.As above-described, use metal-salt, particularly silver salt, be disadvantageous, because be difficult to from product, remove trace-metal, and the photoelectric properties of complex of iridium are had a negative impact.For using mercury, antimony and other metals, situation too.Use mercury salt also relevant with sizable health and environmental risk property.
WO 04/084326 has described in the presence of the auxiliary ligand of metal halogen key that can rupture, through [L 2IrHal] 2The method for preparing tris-ortho-metalated complex of iridium with other aryl-pyridine type ligand reaction.The auxiliary ligand of describing is pyridine, triaryl phosphine and ketone ketone acid salt particularly.Should synthetic also can begin to carry out in two steps from metal halide with single still method.The solvent that uses is a protonic solvent, and particularly terepthaloyl moietie is reflected under the backflow and carries out (in terepthaloyl moietie, promptly at about 197 ℃).Via two steps, from IrCl 3Beginning obtains 60% productive rate.Equally also hope the raising of productive rate here.This method exists in addition needs the shortcoming of under violent condition (197 ℃ of refluxed 3 days), carrying out.Under the situation of responsive ligand, this possibly cause the decomposition of the title complex of ligand or formation.In addition; This reaction conditions is not suitable for the synthetic tris-ortho-metalated different shaped metal title complex of joining; Because ligand exchange always takes place under these reaction conditionss, meaning and can not separate the consistent different tris-ortho-metalated title complex of type of joining, only be antithesis the title complex mixture.
WO 05/042548 has described through [L 2IrHal] 2With the Organometallic derivatives of aryl-pyridine ligand, particularly basic metal or the synthetic different method of joining the type complex of iridium of alkaline earth metal derivative reaction.Here (from [L 2IrHal] 2) begun to obtain to be higher than 95% good yield.Yet there is following shortcoming in this method: it will be via carrying out as the basic metal or the alkaline earth metal derivative of midbody to air and water sensitive; Meaning reaction must carry out under special sfgd.; This possibly mean safety hazard, particularly on plant-scale level.This method does not show the advantage that the type title complex is all joined in preparation, because going on foot via two, this reaction carries out, and midbody [L 2IrHal] 2Must preparation in other step, separation and purifying.Other shortcoming is: the ligand precursor that this method needs only can prepare with the mode of complicacy or be difficult in fact to synthesize usually, and can not form the corresponding Organometallic derivatives of this ligand selectively sometimes.
JP 2004/238379 has described in the presence of alkali through [L 2IrHal] 2React the method for synthesizing complex of iridium with other ligand.The alkali that uses is mineral alkali, alkali metal alcoholates or organic amine preferably.The solvent of pointing out is a polar solvent, particularly terepthaloyl moietie, glycerine, 2-methyl cellosolve, cellosolvo and DMF.Only embodiment has described and has used trolamine in terepthaloyl moietie, to utilize the synthetic of microwave radiation as alkali.
As conspicuous from above-mentioned document, advantageously can obtain the following method that extensively is suitable for, through this method can be simply, high yield and under mild reaction conditions from the synthetic tris-ortho-metalated complex of iridium of the halogenation iridium (III) that is easy to get.Be still necessaryly with respect to significant improvement of prior art, particularly join the synthetic of shaped metal title complex for different.In addition, advantageously obtain simply repeatably to prepare method through the formula title complex.Use is difficult to obtain these title complexs according to the method for prior art, because they are thermodynamic instabilities with respect to corresponding face formula title complex.
Have been found that surprisingly: comprise that the salt existence of at least two Sauerstoffatoms is following if be reflected at its negatively charged ion; In the solvent mixture that comprises organic solvent and at least 5 volume % water, carry out; Under special mild conditions; Begin from two molecular complexs of metal halide or halogenide bridge joint, synthetic tris-ortho-metalated rhodium and complex of iridium and two ortho-metalated palladium and platinum complexes obtain good especially productive rate.This method depends on that the salt that select to add can obtain the face formula selectively and through the complex of iridium of formula, otherwise it is difficult to obtain.In later step, also can change corresponding face formula title complex into through the formula title complex.Therefore, this is first method, and it obtains tris-ortho-metalated complex of iridium with good yield from the hydration iridium halogenide that is easy to get in a step under mild reaction conditions.This result is astonishing especially; Because be known that in the document; On the one hand use the mixture of ethoxy ethanol and water only can cause about 10% productive rate, and on the other hand, pure organic solvent with the violent reaction conditions of alkali request for utilization (through utilizing the microwave radiation activation) with the realization high yield.Therefore, it is not conspicuous that the combination that comprises solvent system and the specific salts of organic solvent and water produces this intense influence to reaction process.In addition, find that this method can not only be used for synthetic complex of iridium, and can be used for synthetic corresponding rhodium, palladium and platinum complex.
The present invention relates to prepare the method for general formula (1) metal complexes,
Figure S2006800458117D00051
General formula (1)
Wherein:
M is Rh, Ir, Pd or Pt;
DCy is in occurring each time; Identical or different, be the cyclic group that comprises at least one neutral ligating atom (preferred nitrogen or phosphorus), via this neutrality ligating atom; Cyclic group and melts combine, and this cyclic group can the one or more substituent R of carrier band; Group DCy and CCy are connected to each other via covalent linkage; In addition, they can further be connected to each other via radicals R;
CCy is in occurring each time, and is identical or different, is the cyclic group that comprises carbon atom or electronegative nitrogen-atoms, through carbon atom or this cyclic group of electronegative nitrogen-atoms and melts combine, and the one or more substituent R of this cyclic group carrier band;
R is identical or different in occurring each time, is F, Cl, Br, I, NO 2, CN, NH 2, NHR 1, N (R 1) 2, B (OH) 2, B (OR 1) 2, CHO, COOH, CON (R 1) 2, SO 3H, C (=O) R 1, P (=O) (R 1) 2, S (=O) R 1, S (=O) 2R 1, P (R 1) 3 +, N (R 1) 3 +, OH, SH has the straight chained alkyl or the alkoxyl group of 1-20 carbon atom, or has side chain or the cyclic alkyl or the alkoxyl group of 3-20 carbon atom, they separately in, one or more non-adjacent CH 2Group can be by-O-,-S-,-NR 1-,-CONR 1-,-CO-O-,-CR 1=CR 1-or-C ≡ C-replaces, and they equally can be by one or more radicals R 2Replace,
Have 5-30 aromatic nucleus atom fragrance or assorted aromatic ring, they can be by one or more radicals R 2Replace, or have aryloxy, heteroaryloxy, the virtue amino or assorted fragrant amino of 5-30 aromatic nucleus atom, they can be by one or more radicals R 2Replace; This be on the identical ring and the two or more substituent R on two different rings each other or and R 1, R 2And/or R 3Can limit other list or polycyclic, aliphatic series or aromatic ring system conversely together;
R 1In occurring each time, identical or different, be H, have the straight chained alkyl of 1-20 carbon atom, or have the side chain or the cyclic alkyl of 3-20 carbon atom, they separately in, be not directly connected to the one or more non-adjacent CH on the heteroatoms 2Group can be by-O-,-S-,-NR 3-,-CONR 3-,-CO-O-,-CR 3=CR 3-or-C ≡ C-replaces, and they can be equally by one or more radicals R 2Replace,
Or having the fragrance or the heteroaromatic ring system of 5-30 aromatic ring atom, they can be by one or more radicals R 2Replace; Two or more here substituent R 1Conversely can be each other or with R, R 2And/or R 3Limit other list or polycyclic aliphatic series or aromatic ring system;
R 2In occurring each time is identical or different, is H, F, Cl, Br, I, NO 2, CN, NH 2, NHR 3, N (R 3) 2, B (OH) 2, B (OR 3) 2, CHO, COOH, CON (R 3) 2, SO 3H, C (=O) R 1, P (=O) (R 1) 2, S (=O) R 1, S (=O) 2R 1, P (R 3) 3 +, N (R 3) 3 +, OH, SH has the straight chained alkyl or the alkoxyl group of 1-20 carbon atom, or has side chain or the cyclic alkyl or the alkoxyl group of 3-20 carbon atom, they separately in, one or more non-adjacent CH 2Group can be by-O-,-S-,-NR 3-,-CONR 3-,-CO-O-,-CR 3=CR 3-or-C ≡ C-replaces, and they can be equally by one or more radicals R 3Replace,
Have 5-30 aromatic nucleus atom fragrance or assorted aromatic ring, they can be by one or more radicals R 3Replace, or have aryloxy, heteroaryloxy, the virtue amino or assorted fragrant amino of 5-30 aromatic nucleus atom, they can be by one or more radicals R 3Replace; This is on the identical ring and the two or more substituent R on two different rings 2Each other or with R, R 1And/or R 3Can limit other list or polycyclic, aliphatic series or aromatic ring system conversely together;
R 3In occurring each time, identical or different is H or aliphatic series or the aromatic hydrocarbon group with 1-20 carbon atom; Two or more here radicals R 3Also can form ring system each other;
M is 2 for M=Pd or Pt, is 3 for M=Rh or Ir;
Said method is carried out through the metallic compound of general formula (2), general formula (3) or general formula (4) and the reaction of general formula (5) compound; It is characterized in that this is reflected under the situation that salt that its negatively charged ion comprises two Sauerstoffatoms exists at least, carries out at least in the solvent mixture that contains at least a organic solvent and 2 volume % water.
MX m*z?H 2O*y?HX Y n[MX p]*z?H 2O*y?HX
General formula (2) general formula (3)
Figure S2006800458117D00071
General formula (4)
Wherein M has the identical implication of describing like general formula (1) with m, below is applicable to other symbol and mark:
X is in occurring each time, and is identical or different, is F, Cl, Br or I;
Y is in occurring each time, and the tetraalkylammonium cation that identical or different is alkali metal cation, alkaline earth metal cation, ammonium cation, have a 4-40 C atom perhaps has the tetraalkyl phosphorus positively charged ion of 4-40 C atom;
P is 4 for M=Pd or Pt, is 6 for M=Rh or Ir;
N is corresponding to the electric charge M of monovalent cation Y, and half the corresponding to divalent cation Y electric charge;
Z is 0-100;
Y is 0-100;
Figure S2006800458117D00081
General formula (5)
Wherein DCy and CCy have the implication of under general formula (1), mentioning.
For the object of the invention, ring-type not only is meant monocyclic but also is the perhaps polycyclic of dicyclo.
If group forms the ring-type system each other, can form condensed fragrance or non-aroma system so thus.Here should stress again clearly, for example can also form ring system each other with CCy and those groups of DCy bonded with different groups.
For the object of the invention, wherein other single H atom or CH 2Group can be by the substituted C of the above-mentioned group of mentioning 1-C 40Alkyl is especially preferably thought and is meant following group: methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec.-butyl, the tertiary butyl, 2-methylbutyl, n-pentyl, sec.-amyl sec-pentyl secondary amyl, cyclopentyl, n-hexyl, cyclohexyl, n-heptyl, suberyl, n-octyl, ring octyl group, 2-ethylhexyl, adamantyl, trifluoromethyl, pentafluoroethyl group, 2; 2,2-trifluoroethyl, vinyl, propenyl, crotonyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, cycloheptenyl, octenyl, cyclooctene base, ethynyl, proyl, butynyl, pentynyl, hexyn or octyne base.C 1-C 40-alkoxyl group especially preferably thinks to refer to methoxyl group, oxyethyl group, positive propoxy, isopropoxy, n-butoxy, isobutoxy, sec.-butoxy, tert.-butoxy or 2-methyl butoxy.Have 1-30 aromatic nucleus atom, also can be by the above-mentioned radicals R of mentioning 2Perhaps R 3The aromatics or the heteroaromatic ring system that replace and can be connected with aromatics or heteroaromatic system through the position of any hope particularly refer to derive from following group: benzene, naphthalene, anthracene, phenanthrene, pyrene, bend, perhaps trans indenofluorene, furans, cumarone, isobenzofuran, diphenylene-oxide, thiophene, thionaphthene, different thionaphthene, dibenzothiophen, pyrroles, indoles, isoindole, carbazole, pyridine, quinoline, isoquinoline 99.9, acridine, phenanthridines, the benzo-5 of Asia puecon, firefly anthracene, naphthacene, pentacene, benzopyrene, biphenyl, biphenylene, terphenyl, inferior terphenyl, fluorenes, spiral shell two fluorenes, tribenzyl-benzene (truxene three polyindenes), different tribenzyl-benzene, dihydro phenanthrene, dihydropyrene, tetrahydrochysene pyrene, cis, 6-quinoline, benzo-6,7-quinoline, benzo-7,8-quinoline, thiodiphenylamine, phenoxazine, pyrazoles, indazole, imidazoles, benzoglyoxaline, naphtho-imidazoles, phenanthro-imidazoles, pyridine-imidazole (pyridimidazole), pyrazine and imidazoles, quinoxaline and imidazoles, oxazole, benzoxazole, naphthalene and oxazole, anthracene and oxazole, phenanthrene be oxazole, isoxazole, 1 also; 2-thiazole, 1,3-thiazoles, benzothiazole, pyridazine, benzo pyridazine, pyrimidine, benzo pyrimidine, quinoxaline, pyrazine, phenazine, 1.5-naphthyridine, nitrogen carbazole, benzo carboline, phenanthroline, 1,2,3-triazoles, 1; 2,4-triazole, benzotriazole, 1,2,3-oxadiazole, 1; 2,4-oxadiazole, 1,2,5-oxadiazole, 1; 3,4-oxadiazole, 1,2,3-thiadiazoles, 1; 2,4-thiadiazoles, 1,2; 5-thiadiazoles, 1,3,4-thiadiazoles, 1; 3,5-triazine, 1,2; 4-triazine, 1,2,3-triazine, tetrazolium, 1; 2,4,5-tetrazine, 1; 2,3,4-tetrazine, 1; 2,3,5-tetrazine, purine, pteridine, indolizine and diazosulfide.
Depend on starting material and ligand, can not only synthesize and all join type and can synthesize the different shaped metal title complex of joining.All join the type title complex and think the compound that is meant wherein only identical ligand and melts combine.Differently join those title complexs that the type title complex is wherein different ligand and melts combine.This not only relates to the ligand with different ligand substruction, and relates to and have same principle construction but can be by substituted ligand differently.If the compound of the compound of the compound of general formula (2) or general formula (3) and general formula (5) reacts, then the shaped metal title complex is all joined in formation usually.If the ligand of the general formula (5) of the compound of general formula (4) and same type reacts, the shaped metal title complex is all joined in then usually same formation.If the ligand of the compound of general formula (4) and dissimilar general formula (5) reacts, then form the different shaped metal title complex of joining.Preferred octahedral different shaped metal title complex of joining is those metal complexess that comprise two kinds of identical ligands ligand different with the 3rd.
Depend on the reaction mode of carrying out, not only face formula but also all can optionally obtain through method of the present invention through the octahedra title complex of formula.
Face formula on the application's meaning or described the octahedral environment of metal M through the formula coordination with six ligating atoms.If three identical ligating atoms occupy gore in the polyhedron of (puppet) octahedral coordination, in (puppet) octahedral coordination polyhedron, occupy other gore with three identical ligating atoms that are different from first ligating atom, then there is the coordination of face formula.Under formula coordinate situation, three identical ligating atoms occupy first warp in the polyhedron of (puppet) octahedral coordination, and three identical but ligating atom that be different from first ligating atom occupies other warp in (puppet) octahedral coordination polyhedron.With reference to three N ligating atoms and three C ligating atom coordinate instances, show below (synoptic diagram 1).Because this definition relates to ligating atom; Do not relate to the ring of these ligating atoms CCy and DCy are provided; So three ring CCy possibly be identical or different with three ring DCy in occurring each time, yet on the application's meaning, be equivalent to the face formula or through the coordination of formula.Identical ligating atom is thought and is meant those that be made up of identical element (for example carbon or nitrogen), no matter whether these elements introduce various structure.This definition is equally applicable to comprise usually the metal complexes of three neutrality and three anion binding atoms, is meant if for example ligand also can be used this definition via neutral nitrogen atom and the coordination of negatively charged ion nitrogen-atoms.
Synoptic diagram 1:
Figure S2006800458117D00101
The coordination of face formula is through the formula coordination
Preferred raw metal is that wherein on behalf of iridium or platinum, symbol M be in particular those of iridium according to the present invention.
The compound of preferred general formula (2) is that wherein symbol z represents 1-10, those of preferred especially 1-3.The compound of preferred general formula (2) is that wherein symbol y represents 0-10 in addition, those of preferred especially 0-3.
The compound of preferred general formula (3) is that wherein symbol z represents 0-10, those of preferred especially 0-3.The compound of preferred general formula (3) is that wherein symbol y represents 0-10 in addition, preferred especially 0-3, those of preferred very especially 0.
Here mark z and y are not necessarily integer, because this title complex also can comprise the water and the HX of nonstoichiometry amount.Because relate to hygroscopic metal-salt, so depend on that batch particularly water-content can change.Yet the ratio of the water in raw material is to not influence of reaction, because a large amount of relatively water joins in the reaction mixture.
The preferred raw metal of general formula (2), (3) and (4) is symbol X wherein in addition, identical or different representative chlorine or bromines in occurring each time, those of preferred especially chlorine.
Preferred ligand is symbol CCy wherein, but those of aromatics or heteroaromatic group that identical or different representatives has 5-20 aromatic ring atom and the one or more substituent R of carrier band in occurring each time.This aromatics or heteroaromatic group CCy also can condense.This is at least one and is positioned at and the ortho position of Dcy bonded key coordinate ligand not, must have unsubstituted carbon atom or NH group, then can with metal link.This group CCy is especially preferably via carbon atom and melts combine.Preferred aryl groups CCy has a 6-20 carbon atom, preferred 6-14 carbon atom, preferred especially 6 or 10 carbon atoms those, they also can be by one or more radicals R replacements.Very special preferred aryl groups is phenyl, naphthyl, anthryl, fluorenyl and phenanthryl, particularly phenyl and naphthyl, and it can be replaced by one or more radicals R separately.Preferred heteroaromatic group CCy has those of at least one heteroatoms and at least two carbon atoms, and wherein the summation of heteroatoms and carbon atom must be at least 5.Said heteroatoms is preferably selected from N, S and/or O.Preferred heteroaromatic group comprises 5-14 aromatic ring atom, preferred especially 5,6,9 or 10 aromatic ring atoms.Preferred especially heteroaromatic group stems from thiophene, pyrroles, furans, imidazoles, pyrazoles, pyridine, pyrazine, pyrimidine, pyridazine, thionaphthene, indoles, carbazole, cumarone, quinoline, isoquinoline 99.9 or quinoxaline, and it can be replaced by one or more radicals R separately.
Preferred ligand is those of the cyclic group of wherein symbol DCy identical or different representative in occurring each time with 5-20 annular atoms in addition, and described annular atoms comprises that at the ortho position with CCy bonded key the neutral nitrogen atom is as ligating atom.Here nitrogen is preferred perhaps is combined in the imines functionality or the part of heteroaromatic system.This DCy ring system comprises at least one nitrogen-atoms and at least two carbon atoms, and the wherein all heteroatomss and the summation of carbon atom must be at least 5.DCy preferably includes and comprises 5-20 aromatic ring atom, preferred especially 5-14 aromatic ring atom, preferred very especially 5,6,9 or 10 aromatic ring atoms.Preferred especially ring-type system DCy is selected from pyridine, quinoline, isoquinoline 99.9, quinoxaline, benzo pyrimidine, 2-naphthazin(e), phenanthridines, oxazole, thiazole, benzoxazoles or benzothiazole; Be in particular pyridine, quinoline, isoquinoline 99.9 or benzo pyrimidine, it can be replaced by one or more radicals R separately.
This is reflected under the situation that adds the salt that comprises two Sauerstoffatoms carries out at least.Here this salt or organic salt or inorganic salt.Zwitterionic compound (so-called inner salt) also is used for the object of the invention and is suitable for method of the present invention.Preferred at least one negatively charged oxygen atom.This Sauerstoffatom is preferably with 1 in addition, 3-, 1,4-or 1; 5-arranges and is combined in (synoptic diagram 2, the central atom that wherein is attached to except carbon also is possible, for example is attached to sulphur, nitrogen or phosphorus) in the salt; Be that their preferred combination are to identical central atom (1; The 3-arrangement), be attached to adjacent central atom (1,4-arranges) and perhaps be attached on the central atom of (central atom) (1,5-arranges) under each situation.This Sauerstoffatom is especially preferably with 1,3-or 1, and 4-arranges, and very especially preferably with 1,3-arranges and is combined in the salt.Also can original position form salt through adding alkali.
Synoptic diagram 2:
Figure S2006800458117D00121
1,3-arranges 1, and 4-arranges 1, and 5-arranges
For the object of the invention, inner salt or zwitter-ion are thought and are meant the compound that comprises that in same molecular at least one contains the anionic group of at least two Sauerstoffatoms and comprises at least one cation group.For example can form the inner salt of the type, the for example reaction between carboxylic acid group and amino in aminocarboxylic acid through acidic group in same molecular and the reaction of the intramolecularly acid-alkali between the base.
Preferred inorganic salt are carbonate, supercarbonate, vitriol, hydrosulfate, sulphite, hydrosulphite, nitrate salt, nitrite, phosphoric acid salt, hydrophosphate, dihydrogen phosphate, borate, particularly basic metal, ammonium and the tetraalkylammonium salt of basic metal, earth alkali metal, ammonium, tetra-allkylammonium, tetraalkyl phosphorus and/or four aryl microcosmic salts.In all these salt, Sauerstoffatom is with 1, and 3-arranges combination.
Preferred organic salt is basic metal, earth alkali metal, ammonium, tetra-allkylammonium, tetraalkyl phosphorus and/or the four aryl microcosmic salts with organic carboxyl acid of 1-20 carbon atom; The formate, acetate, fluoroacetate, trifluoroacetate, trichloroacetate, propionic salt, butyrates, oxalate, benzoate, the pyridine carboxylic acid salt, particularly MeSO that particularly have the organic sulfonic acid of 1-20 carbon atom 3 -, EtSO 3 -, PrSO 3 -, F 3CSO 3 -, C 4F 9SO 3 -, phenyl-SO 3-, adjacent-, or p-methylphenyl-SO 3 -, and alpha-keto carboxylic acid salt, the for example salt of pyruvic acid; β-ketone ketone acid salt, particularly acetyl-pyruvate, β-keto-earboxylic acid salt; For example the salt of beta-ketobutyric acid and pyrocatechol and salicylic salt particularly have those that are up to 20 carbon atoms under each situation.Sauerstoffatom in organic carboxyl acid and organic sulfonate is with 1, and 3-arranges combination, and those in oxalate are not only with 1,3-and with 1; 4-arranges combination, and those in β-ketone ketone acid salt are with 1, and 5-arranges combination; And in β-keto-earboxylic acid salt those are with 1,3-and 1, and 5-arranges combination.
Here carbonyl hydrochlorate and sulphonate can have straight chain, side chain or cyclic substruction, and can be aliphatic series and/or aromatics.They can be replaced or not replace in addition by the radicals R of above-mentioned definition.
An alkali metal salt is thought and is meant lithium, sodium, potassium, rubidium and cesium salt, preferred sodium and sylvite.Alkaline earth salt is thought and is meant beryllium, magnesium, calcium, strontium and barium salt, preferred magnesium salts.Tetraalkylammonium salt is preferably thought and is meant those that have 4-40 carbon atom altogether, particularly tetramethylammonium, Tetrylammonium, tetrapropylammonium and tetrabutylammonium.The tetraalkyl microcosmic salt preferably thinks and is meant those that have 4-40 carbon atom altogether, particularly tetramethyl-phosphorus, tetraethyl-phosphorus, tetrapropyl phosphorus and tetrabutyl phosphorus.Four aryl microcosmic salts are preferably thought and are meant those that have 20-40 carbon atom altogether, particularly tetraphenylphosphonium and tetramethylphenyl phosphorus.Mainly use those to dissolve in the salt in the reaction medium here, preferably those in the reaction medium which 0.001mol/l concentration, preferred especially 0.01mol/l concentration at least, preferred very especially 0.1mol/l concentration at least are dissolved at least.
Preferred inner salt is an aminocarboxylic acid, preferably in neutral medium, is mainly those aminocarboxylic acids, particularly a-amino acid with 2-20 carbon atom of zwitterionic form; For example glycocoll, L-Ala, l-arginine, asparagine, aspartic acid, Stimulina, L-glutamic acid, Histidine, L-LEU, Isoleucine, Methionin, phenylalanine, proline(Pro), Serine, Threonine, tryptophane, tyrosine or Xie Ansuan are similarly β-and gamma-amino acid, for example γ-An Jidingsuan; Aromatic amino acid, for example 2-benzaminic acid, 3-benzaminic acid, 4-benzaminic acid, polyamino carboxylic acid; The for example verivate of YD 30 and YD 30 and the above-mentioned classification compound corresponding N-alkyl aminocarboxylic acid of mentioning, wherein alkyl preferably comprises 1-10 carbon atom; Preferred especially 1,2,3 or 4 carbon atom; N for example, N-dimethylamino acetate, N, N-diethyl amino guanidine-acetic acid, N; N-dimethyl propylene propylhomoserin, 4-N, N-dimethylaminobutyricacid acid or the like.Preferred inner salt is thionamic acid in addition, preferably has 2-20 carbon atom, the thionamic acid of taurine and corresponding N-alkylization for example, and wherein alkyl preferably comprises 1-10 carbon atom, preferred especially 1,2,3 or 4 carbon atom.Preferably through from these compounds, removing these amino acid that one or more protons obtain or the salt of thionamic acid, wherein suitable positively charged ion is the above-mentioned positively charged ion of mentioning in addition.
The preferred mol ratio of the salt of metal and adding is 1: 1-1: 1000, preferred especially 1: 5-1: 300, preferred very especially 1: 10-1: 150.Therefore the mol ratio of the metallic compound of general formula (2) or general formula (3) and the salt of adding is preferably 1: 1-1: 1000; Preferred especially 1: 5-1: 300; Preferred very especially 1: 10-1: 150; The metallic compound of general formula (4) is preferably 1 with the mol ratio that adds salt: 2-1: 2000, preferred especially 1: 10-1: 600, preferred very especially 1: 20-1: 300.
According to the present invention, this is reflected in the solvent mixture that contains organic solvent and water, is preferably carrying out in the solution uniformly.Relate to the salt of solvent mixture, raw material and adding here uniformly, and do not relate to reaction product, described reaction product precipitates from reaction mixture usually.Therefore preferred and water can mixable organic solvent, and particularly those are with the ratio and the mixable organic solvent of water of any hope.These are polar protic and polar aprotic solvent particularly.
Preferred polar aprotic solvent is an alcohol; The alcohol that particularly has 1-5 carbon atom, for example methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol or the trimethyl carbinol perhaps also have glycol or polyvalent alcohol; For example terepthaloyl moietie, Ucar 35, glycerine, polyoxyethylene glycol; For example PEG600 and PEG 1000, and alkoxyl alcohol, for example methyl cellosolve or ethoxy ethanol.
Preferred polar aprotic solvent is the mixable open chain ether of water, for example triglyme, gather (terepthaloyl moietie) dme, the mixable cyclic ethers of water, for example DIOXANE or THF and DMSO, NMP and DMF.
The organic solvents in particular of using is the polar aprotic solvent preferably, preferred very especially cyclic water mixable ether, particularly dioxane.
According to the present invention, the ratio of water is at least 2vol% in reaction medium.The proportional range of water is preferably 5-90vol%, and preferred especially 7-75vol% is preferably 10-60vol% very especially.The water-content of 40-60vol% is suitable especially.
Preferred reaction preferred 40-150 ℃ especially, is carried out under preferred 50-100 ℃ the TR at 20-250 ℃ very especially.These than reaction conditions of the prior art significantly the reaction conditions of milder following advantage is provided: also can with heat and/or chemosensitive ligand carry out this reaction; And ligand exchange reaction does not take place under these temperature, meaning through this method also can high yield, selectivity and purity obtains the different type title complex of joining.Depend on solvent mixture, reaction can be carried out in these temperature refluxed.Therefore, the reaction in the mixture of Zai diox and water is preferably carried out under refluxing.Under the situation of 1: 1 mixture, this temperature of corresponding about 85-90 ℃.This reaction can also for example be carried out in autoclave under pressure.
The raw metal compound concentrations scope of general formula (2) or general formula (3) is preferably 0.5mmol/l-100mmol/l, preferred especially 1-30mmol/l, preferred very especially 2-10mmol/l.The raw metal compound concentrations scope of general formula (4) is preferably 1-1000mmol/l, preferred especially 5-500mmol/l, preferred very especially 10-100mmol/l.
The metallic compound of general formula (2) or general formula (3) and the preferred mol ratio of general formula (5) ligand are 1: 1-1: 60, preferred especially 1: 3-1: 10, preferred very especially 1: 3-1: 8.The preferred mol ratio of the metallic compound of general formula (4) and general formula (5) ligand is 1: 1-1: 100, preferred especially 1: 2-1: 70, preferred very especially 1: 2-1: 50.
Because the common excessive use of ligand, so sometimes even with sizable excessive use, it possibly be suitable then after reaction, reclaiming the latter, particularly synthesizes under the complicated situation in ligand.This for example can carry out through extracting mother liquor with water immiscible solvent.
This reaction is preferably within 1-100h, particularly preferably in carrying out within the 5-50h.Obviously, although reaction conditions is gentle, this reaction is more promptly carried out than the significant reaction of prior art.
For example utilize the microwave radiant energy further to quicken this reaction.The mode of the ortho-metalated reaction of wherein in microwave, carrying out usually for example is described among the WO 04/108738.Yet according to the method for the invention, in order to realize good productive rate, it is not indispensable utilizing microwave radiation.
Method of the present invention can optionally prepare the face formula perhaps through the formula metal complexes.Find particularly to utilize metal carboxylate for example during acetate here, form metal complexes, and when utilizing amino acid, alkylation amino acid, thionamic acid, alkylation thionamic acid and pure inorganic salt, form corresponding face formula metal complexes through formula.
The method of the ortho-metallated metal complexes of the face formula three of preferred preparation general formula (1) in addition; It is characterized in that at first method preparation of the present invention according to foregoing description through the formula title complex, then is converted into this meridianal isomer through reactions step the facial isomer of this title complex.Through energize, particularly heat energy or electromagnetic radiation (uv-radiation, microwave radiation or the like) can make meridianal isomer be converted into facial isomer.Here step of converting can perhaps directly carry out in reaction soln after reaction as single still technology, is perhaps carrying out in independent reactions step through formula metal complexes after separating.To for example be described in (A.B.Tamayo, B.D.Alleyne, P.I.Djurovich, S.Lamansky such as Thompson through the mode that the formula title complex is converted into face formula title complex; I.Tsyba, N.N.Ho, M.E.Thompson; J.Am.Chem.Soc.2003,125,7377-7387).
The present invention relates to this method in addition and be used to prepare Bifunctionalized metal complexes, especially for the purposes of preparation dibromo compound.These are particularly suitable for the monomer as the preparation polymkeric substance.Method of the present invention utilizes various ligands easily to obtain these monomers first.
Because the inventive method can be especially simply, obtain the different shaped metal title complex of joining selectively and with good productive rate; For example by bromine, boric acid; Perhaps for example boric acid glycol ester or the substituted octahedra title complex of boric acid pinacol ester of boric acid ester; These substituting groups are as polymerisable functional group on two in three ligands and on the 3rd ligand, do not have the polymerisable group of carrier band, therefore obtain polymkeric substance, oligopolymer or the dendrimer of the type equally more easily than prior art.Therefore, the Bifunctionalized compound that the invention still further relates to the general formula (1) that obtains through the inventive method is used for preparing the purposes of conjugation, partly conjugated or non-conjugated polymeric thing, oligopolymer or dendrimer.Preferably halogen, particularly bromine or boric acid or boric acid derivatives of the functional group of Bifunctionalized compound here.
The inventive method provides following advantage with respect to prior art:
1. the inventive method can obtain tris-ortho-metalated metal complexes and have fabulous productive rate from one step of metal halide that is easy to get; And the method for prior art begins from more complicated raw material; For example various metal ketone ketone acid salt complexes, perhaps productive rate is obviously poorer.
2. the inventive method additional advantage is gentle reaction conditions.Surprisingly; Because the similar method of prior art (is used microwave radiation at obviously more violent reaction conditions; Reaction under surpassing 190 ℃) carries out under; Said method will for example be carried out under the situation of supercarbonate adding acetyl-pyruvate or mineral alkali, but in reaction mixture, does not comprise water.This water is surprising and the result is unpredictalbe to the influence of reaction, because ethoxy ethanol and water and the reaction do not added in the mixture of salt only obtains 10% yield in the prior art.
3. gentle reaction conditions makes this method also can be used in synthetic metal complexes with heat and/or chemical-sensitive ligand, and these ligands cause undesirable side reaction in art methods.
4. mild reaction conditions makes it possible to the optionally synthetic different shaped metal title complex of joining.These are to be difficult to synthetic according to prior art, produce product mixtures because ligand exchange reaction at high temperature always takes place.Therefore, also be particularly suitable for preparing can be as the monomeric different type title complex of joining in the polyreaction for this method.
5. the inventive method can be simply and is optionally synthetic through the formula title complex, otherwise only can obtain with the mode of complicacy and very accurately controlling under the reaction conditions through the formula title complex.Have red shift because compare the luminous of meridianal isomer with facial isomer, so it is preferred for producing emitting red light.If hope, also can be converted into corresponding face formula title complex selectively through the formula title complex.
Illustrate in greater detail the present invention through following examples, but do not hope the present invention is limited to said embodiment.Based on the present invention, under the situation that does not need other creative work, organic those of ordinary skill with the synthetic field of organic metal can carry out this reaction to other systems.Particularly, under the situation that does not need other creative works, this method can be applicable to different substituted systems, perhaps also is applicable to the aryl that comprises other or the system of heteroaryl rather than phenyl, pyridine, isoquinoline 99.9 or benzo pyrimidine.
Embodiment
Only if point out in addition, below synthesize under shielding gas atmosphere and carry out.Iridium chloride (III) hydrate can be bought from Heraeus, confirms general molecular formula IrCl according to iridium and water-content 3* H 2O.Simple substituted 2-phenylpyridine can be bought from Aldrich or ABCR, perhaps through the preparation of normative document method.
Comparative example 1: synthesizing under the situation of not adding water
500ml De diox is joined 10mmol IrCl 3* H 2In the 2-phenylpyridine of O, 60mmol and the sodium acetate mixture of 300mmol, this mixture stirs 30h at 80 ℃.This is reflected in the uniform solution and can not carries out.Formation can not be discerned the settling of compsn.Can not isolate three ortho-metallated metal complexess.
Comparative example 2: synthesizing under the situation of not adding salt
The water of 500ml De diox and 500ml joins 10mmol IrCl 3* H 2In the mixture of the 2-phenylpyridine of O and 60mmol, this mixture stirs 30h at 80 ℃.After the cooling, utilize suction filtration to go deposition.Yield with about 90% obtains the complex of iridium of dimerization chloro bridge joint, [PhPy] 2IrCl 2Ir [PhPy] 2
Embodiment 1: from IrCl 3* H 2O is synthetic all to join type through formula metal complexes-general synthesis step
Organic solvent and water join 10mmol IrCl 3* H 2In the mixture of the general formula of O, 60mmol (5) ligand and salt, this mixture stirs 30h at 80 ℃.Ligand structure, salt, solvent and amount separately and productive rate are listed in the table 1 together.After the cooling; Cross the elimination deposition with suction (P4); Wash three times with the 50ml1N aqueous hydrochloric acid of 50ml and the alcoholic acid mixture of 150ml each time; 100ml water and 100ml alcoholic acid mixture with 50ml washs three times each time, uses the 50ml washing with alcohol each time three times, and be dry under 70 ℃ of decompressions.Obtain degree of purity of production through this method, under situation about not being further purified, according to 1H-NMR is at least 99.0%.
Figure S2006800458117D00221
Figure S2006800458117D00231
Embodiment 2: from IrCl 3* H 2The synthetic profile formula metal complexes-general synthesis step of all joining of O
Organic solvent and water join 10mmol IrCl 3* H 2In the mixture of the general formula of O, 300mmol (5) ligand and salt, this mixture stirs 30h at 80 ℃.Ligand structure, salt, solvent and amount separately and productive rate are listed in the table 2 together.After the cooling; Cross the elimination deposition with suction (P4); 50ml 1N aqueous hydrochloric acid and 150ml alcoholic acid mixture with 50ml washs three times each time; 100ml water and 100ml alcoholic acid mixture with 50ml washs three times each time, uses the 50ml washing with alcohol each time three times, and be dry under 70 ℃ of decompressions.Obtain degree of purity of production through this method, under situation about not being further purified, according to 1H-NMR is at least 99.0%.
Figure S2006800458117D00251
Figure S2006800458117D00261
Embodiment 3: from IrCl 3* H 2O utilizes and adds the synthetic profile formula metal complexes-general synthesis step of all joining of amino acid/thionamic acid
Organic solvent and water join 10mmol IrCl 3* H 2In the mixture of the general formula of O, 60mmol (5) ligand and amino acid or thionamic acid, this mixture stirs 30h at 80 ℃.Ligand structure, amino acid or thionamic acid, solvent and amount separately and productive rate are listed in the table 3.After the cooling; Cross the elimination deposition with suction (P4); 50ml 1N aqueous hydrochloric acid and 150ml alcoholic acid mixture with 50ml washs three times each time; 100ml water and 100ml alcoholic acid mixture with 50ml washs three times each time, uses the 50ml washing with alcohol each time three times, and be dry under 70 ℃ of decompressions.Obtain degree of purity of production through this method, under situation about not being further purified, according to 1H-NMR is at least 99.0%.
Figure S2006800458117D00281
Figure S2006800458117D00291
Figure S2006800458117D00301
Embodiment 4: all join type through formula and the different shaped metal title complex-general synthesis step of joining from the dimerization complex of iridium is synthetic
The water of 500ml De diox and 500ml joins in the mixture of ligand and 300mmol sodium acetate of dimerization complex of iridium, 40mmol general formula (5) of 5mmol general formula (4), and this mixture stirs 30h (embodiment 4a)-4f) down at 80 ℃).Perhaps, the water of 50ml De diox and 50ml joins in the mixture of ligand and 30mmol sodium acetate of dimerization complex of iridium, 6mmol general formula (5) of 0.5mmol general formula (4), and this mixture stirs 30h (embodiment 4g)-4t) down at 80 ℃).Under situation separately, obtain accordingly through the formula title complex.Accurate structure of initial title complex and ligand and productive rate are shown in the table 4.After the cooling; Cross the elimination deposition with suction (P4); 50ml 1N aqueous hydrochloric acid and 150ml alcoholic acid mixture with 50ml washs three times each time; 100ml water and 100ml alcoholic acid mixture with 50ml washs three times each time, uses the 50ml washing with alcohol each time three times, and be dry under 70 ℃ of decompressions.Obtain degree of purity of production through this method, under situation about not being further purified, according to 1H-NMR is at least 99.0%.
The dimerization complex of iridium of general formula (4) can use as document (K.A.King, P.J.Spellane, R.J.Watts, J.Am.Chem.Soc.1985,107, the method preparation described in 1431-1432), for example:
7, and 7-dimethyl--8-fluoro dibenzo [de, h] quinoline (like the description in WO05/033244 preparation) (4.0g, 15.20mmol, 2.1eq.) and IrCl 3* H 2(2.55g, the 7.24mmol) suspensoid in 120ml ethoxy ethanol and 40ml water stir 16h to O under 130 ℃ of inert atmospheres.Descended the elimination precipitated solid at shielding gas, water (100ml), methyl alcohol (100ml), diethyl ether (50ml) and hexane (100ml) wash, and obtain the orange red powder of 3.84g (2.55mmol), are equivalent to 70.6% of theoretical value.
Table 4:
Figure S2006800458117D00321
Figure S2006800458117D00331
Figure S2006800458117D00341
Embodiment 5: from synthetic profile formula and the different type complex of iridium-general synthesis step of joining of all joining of dimerization iridic compound
The water of 500ml De diox and 500ml joins the dimerization complex of iridium of 5mmol general formula (4), the ligand of 40mmol general formula (5) and the N of 300mmol, and in the mixture of N-N-methylsarcosine, this mixture stirs 30h down at 80 ℃.Perhaps; The water of 50ml De diox and 50ml joins the dimerization complex of iridium of 0.5mmol general formula (4), the ligand of 6mmol general formula (5) and the N of 30mmol; In the mixture of N-N-methylsarcosine, this mixture stirs 30h (embodiment 5f)-5s) down at 80 ℃).Form corresponding face formula title complex.Accurate structure of this title complex and ligand and productive rate are shown in the table 5.After the cooling; Cross the elimination deposition with suction (P4); 50ml1N aqueous hydrochloric acid and 150ml alcoholic acid mixture with 50ml washs three times each time; 100ml water and 100ml alcoholic acid mixture with 50ml washs three times each time, uses the 50ml washing with alcohol each time three times, and be dry under 70 ℃ of decompressions.Obtain degree of purity of production through this method, under situation about not being further purified, according to 1H-NMR is at least 99.0%.
Table 5:
Figure S2006800458117D00351
Figure S2006800458117D00361

Claims (17)

1. method for preparing general formula (1) metal complexes,
Figure FSB00000855047800011
General formula (1)
Wherein:
M is Ir;
DCy is in occurring each time; Identical or different; It is heteroaromatic group with 5,6,9 or 10 aromatic ring atoms; Said heteroaromatic group contains the neutral nitrogen atom as ligating atom, and wherein said nitrogen is the part of heteroaromatic system, and said heteroaromatic group can the one or more substituent R of carrier band; Group DCy and CCy are connected to each other via covalent linkage; In addition, they can further be connected to each other via radicals R;
CCy is in occurring each time; Identical or different; They be aromatics or heteroaromatic group, and said aromatics or heteroaromatic group can the one or more substituent R of carrier band, and said aromatics or heteroaromatic group are incorporated into metal M via carbon atom with 6 to 10 aromatic ring atoms;
R is identical or different in occurring each time to be F, Cl, Br, I, CN, N (R 1) 2, having the straight chained alkyl or the alkoxyl group of 1-20 carbon atom, or have side chain or the cyclic alkyl or the alkoxyl group of 3-20 carbon atom, they equally can be by one or more radicals R 2Replace,
Or having the aromatic series ring system of 5-30 aromatic ring atom, they can be by one or more radicals R 2Replace; This is on the identical ring and the two or more substituent R on two different rings can limit other list or polycyclic, aliphatic series or aromatic ring system each other conversely;
R 1In occurring each time, identical or different, be straight chained alkyl, or have the side chain or the cyclic alkyl of 3-20 carbon atom with 1-20 carbon atom, its in separately one or more non-adjacent, be not connected directly to heteroatomic CH 2Group can be replaced by-O-, and they equally can be by one or more radicals R 2Replace;
R 2In occurring each time, identical or different is H, F, Cl, Br, I, CN, N (R 3) 2, having the straight chained alkyl or the alkoxyl group of 1-20 carbon atom, or have side chain or the cyclic alkyl or the alkoxyl group of 3-20 carbon atom, they can be equally by one or more radicals R 3Replace;
R 3In occurring each time, identical or different is H or aliphatic series or the aromatic hydrocarbon radical with 1-20 carbon atom; Two or more here radicals R 3Also can form ring system each other;
M is 3;
Said method is carried out through the metallic compound of general formula (2), general formula (3) or general formula (4) and the reaction of general formula (5) compound,
MX m＊z?H 2O＊yHXY n[MX p]＊z?H 2O＊y?HX
General formula (2) general formula (3)
Figure FSB00000855047800021
General formula (4)
Wherein M and m have like the described identical meanings of mutual-through type (1), and below explanation is applicable to other symbol and mark:
X is in occurring each time, and is identical or different, is F, Cl, Br or I;
Y is in occurring each time, and the tetraalkylammonium cation that identical or different is alkali metal cation, alkaline earth metal cation, ammonium cation, have a 4-40 C atom perhaps has the tetraalkyl phosphorus positively charged ion of 4-40 C atom;
P is 6;
The electric charge M of the corresponding monovalent cation Y of n, and corresponding divalent cation Y electric charge M's is half the;
Z is 0-100;
Y is 0-100;
Figure FSB00000855047800031
General formula (5)
Wherein DCy and CCy have the implication of under general formula (1), mentioning,
It is characterized in that under this situation that is reflected at the salt that exists its negatively charged ion to comprise at least two Sauerstoffatoms; In the solvent mixture that contains at least a organic solvent and at least 2 volume % water, carry out, said organic solvent be selected from alcohol, can be miscible with water open chain or cyclic ether, DMSO, NMP or DMF.
2. according to the method for claim 1; It is characterized in that as starting compound; The compound reaction of the compound of the compound of general formula (2) or general formula (3) and general formula (5); All joined the shaped metal title complex, it is characterized in that perhaps the shaped metal title complex is all joined in the ligand reaction of general formula (5) of compound and the same-type of general formula (4), or the compound that it is characterized in that general formula (4) reacts with the ligand of dissimilar general formula (5) and obtains the different shaped metal title complex of joining.
3. claim 1 or 2 method is characterized in that in the compound of general formula (2), symbol z represents 1-10, and symbol y represents 0-10 and it is characterized in that in the compound of general formula (3), symbol z represents 0-10, and symbol y represents 0-10.
4. according to the method for claim 1 or 2, it is characterized in that in the raw metal of general formula (2), (3) and (4) that symbol X represents chlorine or bromine identical or differently in occurring each time.
5. according to the method for claim 1 or 2, it is characterized in that: the salt of adding is organic salt or inorganic salt or zwitterionic compound.
6. according to the method for claim 1 or 2, it is characterized in that Sauerstoffatom with 1,3-, 1,4-or 1, the mode that 5-arranges is combined in the salt.
7. according to the method for claim 1 or 2; It is characterized in that the inorganic salt that add are carbonate, supercarbonate, vitriol, hydrosulfate, sulphite, hydrosulphite, nitrate salt, nitrite, phosphoric acid salt, hydrophosphate, dihydrogen phosphate or borates of basic metal, earth alkali metal, ammonium, tetra-allkylammonium, tetraalkyl phosphorus and/or four aryl phosphorus; And/or it is characterized in that the organic salt that adds is the organic carboxylate with 1-20 carbon atom of basic metal, earth alkali metal, ammonium, tetra-allkylammonium, tetraalkyl phosphorus and/or four aryl phosphorus, the organic sulfonate with 1-20 carbon atom, β-keto-earboxylic acid salt, β-ketone ketone acid salt, β-keto-earboxylic acid salt, pyrocatechol and salicylic salt; And/or it is characterized in that the inner salt that adds is an aminocarboxylic acid, perhaps it is characterized in that using through removing the salt of these compounds that one or more protons obtain.
8. claim 1 or 2 method, the mol ratio that it is characterized in that the salt of metal and adding is 1: 1-1: 1000.
9. claim 1 or 2 method, it is characterized in that this is reflected in the homogeneous phase solution carries out.
10. claim 1 or 2 method is characterized in that the organic solvent that uses is polar protic and/or polar aprotic solvent.
11. the method for claim 1 or 2, the proportional range that it is characterized in that water in the reaction medium is 5-90vol%.
12. the method for claim 1 or 2 is characterized in that the raw metal compound concentrations scope of general formula (2) or general formula (3) is 0.5mmol/l-100mmol/l, the raw metal compound concentrations scope of general formula (4) is 1-1000mmol/l.
13. the method for claim 1 or 2 is characterized in that the mol ratio of ligand of iridic compound and the general formula (5) of general formula (2) or general formula (3) is 1: 1-1: 60, the mol ratio of the iridic compound of general formula (4) and general formula (5) ligand is 1: 1-1: 100.
14. according to the process of claim 1 wherein that said organic solvent is selected from divalent alcohol.
15. according to the process of claim 1 wherein that said organic solvent is selected from polyvalent alcohol.
16. method for preparing face formula metal complexes; This face formula metal complexes has as in the general formula described in the claim 1 (1); It is characterized in that carrying out according to each described preparation among the claim 1-15 then carrying out meridianal isomer is converted into the reactions step of the facial isomer of this title complex through the method for formula title complex.
17. each described method is used to prepare the purposes that is suitable for as monomeric Bifunctionalized compound among the claim 1-16.
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